Color couplers containing isophthalic acid radicals



Patented Sept. 15. 1953 COLOR COUPLERS CONTAINING ISO- PHTHALIC ACID RADICALS Fred C. McCrossen, Stanley M. Parmerter, and Arnold Weissberger, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application July 31, 1952, Serial No. 301,962

7 Claims. (01. 95-6) This invention relates to color photography, appear from the following description of our inand particularly to color couplers for use in phovention.

tographic emulsions. These objects are accomplished by using as the The use in color photography of color-forming coupler a compound having the formula:

Do conic ONE-Q [NBC o(oH,).].-,o ONH H; K II a o o 2 5 in compounds which react with the oxidation or where development product of primary aromatic amino developing agents to form colored images upon photographic development is well known. The coupler compounds employed in this way may be (CH2)2CONH added to the developing solution or incorporated in the sensitive emulsion. 4CONH When used in the emulsion, the couplers must be soluble in the medium in which they are ino(CH2)3CONH corporated. In the case of direct incorporation CH CHCONH in gelatin or other hydrophilic medium, as in Fischer U. S. Patent 1,102,028, the couplers must 2333 2; ff z g g g g g an have groups rendering them water-soluble, such nil or 2 I 5- p 5 as carboxylic acid groups. In the case of incor- U poration in an organic solvent, as in Marines and i Godowsky U. S. Patent 2,304,940 or Jelley and radlcal I is connected to X in the meta or para Vittum U. S. Patent 2, 22,0 7, the couplers must position, and radical II is substituted in the posi. be soluble in the organic solvent used to dissolve tion ortho or meta t X,

them We have found that the radical of isophthalic In the manufacture of emulsions containing acid is a valuable solubilizing component for couplers, considerable difliculty has been encounplers which are incorporated directly in geltered in urifying couplers containing carboxylic atin emulsions, but compounds containing this acid groups, prior to incorporating them in the radical are difficult to purify by recrystallization. emulsion. Because of the presence of the carbox- If the esters of phthalic acid are used instead of ylic acid radical, soluble salts are formed which the free acid, the compounds may be purified by are difficult to urify by ecrystallization. This is recrystallization, and the esters hydrolyzed to the especially true if there aretwo or more carboxylic free acid before incorporation in the gelatin emulacid groups in the m01ecu1e V r sions. The compounds are then introduced into It is therefore an object of the present inventhe emulsion as an alkali metal salt, usually the tion to provide a novel class of color couplers sodium Salt. which can be readily purified by recrystallization;., The isophthalic acid esters of the couplers may A further bject i to provide color couplers which also be incorporated in the emulsion in solvent can be incorporated in elatin emulsion either by dispersion, as described in Mannes and Godowsky direct incorporation or by dispersion when dis-' U. S. Patent 2,304,940 and Jelley and Vittum U. S.

solved in organic solvents. Other objectswill Patent 2,322,027,

QGOGEBCONHQNHQ 0,

CuHu

HAO HQN Na 0 Ac COCH In a 5-1. flask, equipped with a mechanical 4o stirrer and condenser carrying a drying tube and a thermometer, were placed 157 g. (0.75 mole) of methyl-5-amino-isophthalate and 1 l. of glacial acetic acid. The-mixture was heated to 60 C. and 300 g. (0.74 mole) of crude (2,4-di-tert-.-amylphenoxy)-3-nitrobenzoyl chloride in 500 ml. of glacial acetic acid was added to it all at once, followed by 62 g. (0.76 mole) of anhydrous sodium acetate. The mixture was heated on the steam bath with stirring for 1.5 hrs. longer.

There was practically complete solution for a short time and then the sodium chloride formed came out of solution in very fine crystals. The reaction was stopped, the sodium chloride filtered out by gravity while the solution was still hot, and the filtrate diluted with 200 ml. of boiling water and let stand overnight. The next morning the reaction wascooled to 15 C. and the white crystalline product filtered. It was slurried in 3 l'. of; cold water, filtered again and washed as free of acetic. acid as desired with cold water.

The dry material melted at l12-114 C. and was pure enough to use in the next step.

Methyl-5 [4' (2",4"-di-tert.-amylpheno:cw -3'- aminobenzamtdo] -zsophthalate C sHu OOOGH;

ncownmc ONH OOCHI A 12-1. wide mouth fiask was. equipped with a mechanical stirrer and two wide bor coil condensers. In it were placed 380 g. (0.645 mole) of methyl 5E4(2",4'"-di-tert.-amylphenoxy) 3' nitrobenzamido]isophthalate and 4.5 l. of acetic acid, and the mixture was heated to, reflux with vigorous stirring. At this point. the source of heat was removed and 380 g. of active iron (Fe) was added in 40-50-g; portions through one oi! the condensers. A very vigorous reaction took place on the addition of the iron, but the two water-cooled condensers were sufiicient to control it, if the iron is added in a period of 15 min. A more rapid addition of the iron would require external cooling of the flask, which might be accomplished by playing a jet of running water on it. After the reaction had subsided somewhat, heating was again applied and vigorous refluxing continued for 10 min. longer. The reaction mixture was allowed to cool just below its boiling point and filtered free of the excess iron, excludin air as much as possible. Hot (just below its boiling point) 50% acetic acid (4.5 l.) was added to the filtrate and the flask was shaken by hand for complete mixing, and stoppered immediately. The solution was allowed to cool spontaneously with occasional shaking and finally let stand overnight.

The precipitate formed (just off-white needles) was filtered and washed successively with 50%, 25%, 10% and 5% acetic acid, about 4 l. of each. It was then freed of any acetic acid, either by slurrying in or washing with water. The hot oven-dried product melted at 210-212" C. and was of excellent quality. Yield 320 g. (88.5%).

Methyl-5 [4' (2",4"-di-te1't.-amylpheno:cy) -3' (4- nitrophenoryacetamido) benzamidoj -isophthalate 17TH: B010 I 7 f C5Hn C 03011;

OjGHI IL'HCOCHzOONO:

Methyl 5[4(2",4" di-tert.-amylphenoxy)- 3' aminobenzamido] isophthalate 99 g. (.177 mole) was suspended in 1 l. of glacial acetic acid and heated to 60 C. on a steam bath in a 2-1. flask with occasional shaking. To it were added successively 38 g. (.177 mole) p-nitrophenoxyacetyl chloride and 20.5 g. (.25 mole) of anhydrous sodium acetate. The mixture was heated on a steam bath for 1 hr. under a condenser carrying a drying tube.

There was practically complete solution at first and then a very fine precipitate of sodium chloride was formed. The'hot solution was filtered by gravity and allowed to cool, slowly at first until crystallization was well on'the way, and finally by external cooling to 15 C. with stirring. The solid formed was filtered, slurried with 2 l. of water, filtered again and washed free of acetic o'snoO-o CHzC 01mm HZN acid with water. The dry product melted at 55 208-210 C. Yield 100.5 g., 77% of theory.

Methyl ,-l[4(2,4" dz -,tert. amylphenoxy) 3' (-4 aminophenowyacfitamido) -ben2amido] isophthalate OOQCHI sHu NHCOGHO Methyl 5[4'(2",4" di-tert-amylphenoxy)-; 3 (4 -nitrophenoxyacetamido) -benzamidol -iso'- phthalate 50 g. (.064. mole) and 200 ml. of absolute alcohol were charged into a 375-ml. capacity magnesia bottle. To'it was added 2 g. of sodium carbonate and about 3 .gf of Raney nickel catalyst. The bottle was placed on a Parr hydrogenating machine and a pressure of about 50 lbs. of hydrogen was applied on the system. The bottle was shaken while it was externally heated y with a'jet of steam.

Reduction started very shortly and within min. the required amount of hydrogen was taken up. The bottle was allowed to cool and the reaction mixture was filtered by gravity and let stand overnight in a stoppered vessel. The partly crystallized reaction mixture was cooled to about 10 in-anicebath andthe white crystalline solid was filtered and washed once with m. of cold alcohol and dried. The dry product weighed 39 g. and melted at 17l-172 C. Yield 86%.

0. (4 methomybenzoyl) -4-{a-[2 (2,4 (ii-tertamylphenoxy) 5 (3,5- dicarbomethoxyphenylcarbamyl) phenylcafliiuhyl] memory} acetanilz'de V l l OOH2CONHO ooiofli Ct u M dozen.

CsHu

In a 1-liter flask were placed 35.5 g. (0.05mo1e) of methyl 5-'[4-(2",4"-di-tert-amylphenoxy)- 3' (4' aminophenoxyacetamido) benzamidolisophthalate and 500 cc. of histological xylene. The solution was heated to boiling before 11 g. (0.05

mole) of ethyl p-methoxybenzoylacetate was NHCOCHzO-ONO: 7

ride and o-methoxybenzoyl acetate in place of,

p-methoxybenzoyl acetate.

The preparation of compound 6 is described in application Serial No. 301,961, filed concurrently herewith by McCrossen, Salminen and Weissberger.

The following example illustrates the method of hydrolysis of the ester of the coupler and incorporation in a gelatin emulsion:

3.7 grams of compound 1 were dissolved in a mixture of 15 cc. of 95 per cent ethyl alcohol and 7.5 cc. of 20 per cent sodium hydroxide solution.

The mixture was warmed gently (if necessary) to complete solution of the coupler and then poured into 200 cc. of water at 40 C. If desired, the mixture may be added directly to a gelatin solution. The resulting solution was brought to a pH of 6 to 7 by addition of 2 per cent citric acid solution. The coupler solution was then mixed with a suitable amount of melted silver halide gelatin emulsion e. g. 400 cc. of a positive type gelatino silver halide emulsion at 40 C. After OCH;

coating, the emulsion layer thus obtained may be Go 0 0 H20 0 NH@ :[NHC or CHillL-xC-ONH-Q subjected to the usual exposure and processing steps of color photography.

In hydrolyzing the couplers other means may be used such as acid or alkaline hydrolysis in lower aliphatic alcohol or aqueous media provided thatv the conditions employed do not cause splitting of the coupler at points in the molecule such as at the -NHCO linkage.

The following example illustrates incorporation of the methyl ester of the coupler in solvent dispersion in a gelatin emulsion:

A solution of 7.5 grams of compound 1 in 15 Q6130 m0 0 N grams of 1,2-dimethoxy benzene was added to 200 cc. of water containing 2.0'grams of the wetting agent Gardinol WA. The whole mixture was stirred to effect preliminary emulsification, then passed through a colloid mill several times while the temperature of the solution and the mill was maintained at about 20 C. In this way a very stable and very fine .emulsionwas obtained which was added to 1000 cc. of a melted silver halide gelatin emulsion. The emulsion containing the added coupler dispersion was coated on a suitable support, set and dried in the usual manner. On exposure and development of this emulsion with a developing solution employing 2-amino-5-diethylaminotoluene as the developing agent and subsequent removal of silver, a yellow dye image was obtained.

The following developing solution is suitable for developing silverhalide emulsion layers containingthe couplers incorporated either directly in the emulsion or in solvent dispersions:-

Grams 2 amino 5 diethylaminotoluene hydrochloride 2 Sodium sulfite 2 Sodium carbonate 2 Potassium bromide 2 Water to '1 liter.

It will be understood that the examples and modifications set forth herein are illustrative only and that our invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. A gelatino-silver halide emulsion layer containing a coupler compound having the formula (IJOOZ COO M 2,652,329 "11 1 3. A gelatino-silver halide emulsion layer conl I taining a coupler compound having the formula CONH l QQOCEGONHOOONH ('JQOM Where M is an alkali metal.

4. A gelatino-silver halide emulsion layer con taining a coupler compound having the formula COOM Q-COCECONHQ w JQNHQ 4, V

CH1 H=CH00NH 7 7 00M ooNn' Q0 0011,?) ONHOCHaO ONE-Q 00M V Q- sHu Where M is an alkali metal.

5. A gelatino-silver halide emulsion layer containing acoupler compound having the formula v V (300M Q0 0 cmc ONHQ CONHQ 0H, ONH 00M sHu whereM an alkali metal. V e

6. A gelatino-silver halide emulsion layer. containing a coupler compound having the formula where alkali inefial. i a j 2,652,329 13- 14 7. A gelatino-silver halide emulsion layer con-- taining a coupler compound having the formula (300M (ZONE H30 0--0 001110 ONE-O0 011,0 ONHO 0 0M sHu aHu where M is an alkali metal.

FRED C. MCCROSSEN.

STANLEY M. PARMERTER.

ARNOLD WEISSBERGER.

No references cited. 

1. A GELATINO-SILVER HALIDE EMULSION LAYER CONTAINING A COUPLER COMPOUND HAVING THE FORMULA 